Water-insoluble azo-dyestuffs



Patented Aug. 29, 1933 I I p. g f

WATER-INSOLUBLE AZO-DYESTUFFd Erwin Hofla andPaul Jiirg, Frankfort-on-the: Main-Hochst, Germany, assignors to General Aniline Works, Inc, New York, N. -Y., a cor-' porationof Delaware a H No Drawing. Application January 30, 193 0, get-i111 No. 424,732,- and in Germany February Claims. (01. 260-84) The present invention relates towater-insoluin water, as, for instance, sulfo-groups or carble azo-dyestufis, more particularly itrelates to. boxylic acids groups. The dyestuffs vcan be'pi'onew azo dyestuffs of the following, probable forduced onthefiber as 'well as in substanceoriii mula: r thepresence of any of the usjual substrata which a are adapted for the production 'of lakes. 1F

The following examples serve to illustrate the invention, but they are not intended to limit it thereto: 1: 1

(1) grams of cot'ton ar'e impregnated with 10 I HO a grounding liquor.- preparedas follows:

2.3-hydroxynaphthoic acid arylamines; Thos'e of 4.5 "grams of 2-3- hydroxynaphthoic acid-5'- chloro-fl"-methyl-2ani1ide, 9 grams of Turkey .red oil, and 4.5-gramsof caustic soda solution of 34 B5: are dissolved in ,lpqs ccm of boiling water; to the solution are added ifiiccm of formaldehyde' of 40' c'ntF-s'tren'g'th and Y the whole is wherein the R'sstand for residues of the benzene or naphthalene series, and X means a di rect linkage existing between the two residues R or it represents'the group ,N =N. l We have found that polynuclearor condensed aromatic systems, which contain in one or the v nuclei a free amino-group andvin another nucleus made watter u g 31 3 an arylamino-group, represent diam-components johns lmpmglla' ed has gen squeeze e which yield valuable dyestuffs when cou led withg produoedma q b as p v.

' 2.7,, grams of lam na-14' phenylammodlphenyl and 3 com of hydrochloric. acid of 722 B are boiled'together with 100 com or (water, cooled on ice to 10 C. and diazot i zed with 150cm of the said bases, whose nonarylated parent productsthat is such as contain twofree amino groups-are capable of forming substantive azoa dyestufis, have the remarkable property of yield- SPdmm mtnte To th1 s d fl f 5 mg azodyestufis of particularly deep shads V tlon are added 10 grams of. crystallized sodium Bases of the said kind are generally capable of w f fi 9 9 a t f m yielding by the action of 2 molecular proportions mm? F Q Q-a 3337 9 5 a of sodium nitrite in acid media nitrosodiazo-com- Water t VQQPPFP H pounds which give red to reddish-bxowridyeirigs dyed 0mm yam I c e m "30 when coupled with2.3-hydroxynaphthoic acid it'is i n f treated a -h u ii l arylamines'; these dyeings which are probably boiling 'bathbontaining? 9 iOnfQ 3 E n Q1, produced by'the formation of nitroso-azo-dye- Soap grams Pfnsodlum q a f' 2 grams stufis, are transformed when after-treated withfla of h ny em t u li a 1111000 7 suitable reducing agentor, in'some cases; with a" @6111 rinsed again and d e The dyedv saponifying agent, into dyeingsof the simple matllial which at firs cl qa um azo-d'yestufisg'that is of the dyestuffs which do when after-treated; a p, very rg f lf fi k i not contain the nitroso-group. r 7 blue tint of very good fastness to washing and :The bases can be substituted'in' the aryl nuclei good. fastness to chlorine and to kier boiling. in any desired manner, but they mustinot co1i- The new dyestuff is a dark powder and has the 40 taint-any group rendering the dyestufis soluble following probable formula: 9 1

(2)By substituting 4.5 grams of 2.3-hydroxynapthoic aoid-4-chloro-1-anilide for the 4.5-

'grams of 2.3 hydroxynapthoic acid-5' -chloro- 1'-methyl-2-anilide used in Example 1, a dyestuif of similar properties is obtained. The new dyestuff is a dark powder and has the following probable formula:

The following dyeing process is applied amples 3-7:

in Ex- (3) A. grounding liquor 4.5 grams of 2.3-hydroxynaphthoic"acid-5- g gmcam chloro-l-methyl-2'-anilide, 9 com of Turkey red oil of 50 per cent strength, 9 com of caustic soda solution of 34 B, 200 com ofboiling water, 200 com of cold Water, 2.25 com of formaldehyde of 30 percent. strength, the whole being madeup with water to 1000 ccm.

. n. Dyebath.

2.9 grams of phenylamino-benzene-azo-aniline of the formula I V are treated with 3.8 com of hydrochloric acid of 22 B and 15 com of sodium nitrite (solution 1:10) whereby a nitroso-diazo-compound is obtained. After half-an-hour the solution is neutralized with 10 grams of sodium acetate (solution 1:5) 25 grams of dissolved common salt are added and the whole is made up to 1 liter.

There is obtained a garnet dyeing which turns intense black when after-treated, The newdyestuff is a dark powder and has the probable formula:

(4) A. Grounding liquor 2.5 grams of ZB-hydrdxynaphthoic acidlnaphthylamide, 10 com of Turkey red oil of 50 per cent strength, 7.5 ccm of caustic soda solution of 34 B, 200 com of boiling water, 200 com of cold water, and 125 com of formaldehyde 01 30 per cent. strength are made up with water to 1 liter.

B. Dyebath- -The same as in Example) There is obtaineda garnet dyeing which turns intense black when after-treated. The new dyestuff is a dark powder and has the following probable formula: Y

(5) A. Grounding liquor 7.5 grams of 2.3-hydroxynaphthoic acid anilide, 15 com of Turkey red oil of 50 per cent. strength,

I 11.5 com of caustic soda solution of 34 B, 200

com of boiling water, 200 com of cold water, 3.75 com of formaldehyde of 30 per cent. strength are made up with water to 1' liter.

B. DyebathThe same as inExample 3 There is obtained a garnet dyeing which turns an intense deep black when after-treated. The

new dyestuff is a dark powder and ha's the follow ing probable formula: v

(6) For the 4.5-grams of 2.3 hydroxynaphthoic acid-5'-chloro-1'-methyl-2-anilide used for the.

grounding in Example 3, there is substituted the corresponding quantityof (a) 2.3-hydroxynaphthoic acid-5'-chloro-1'- methyoxy-2'-anilide (b) 2.3 -hydroxynaphthoic acid 4' chloro -1 methoxy-2-anilide (c) 2.3-hydroxynaphthoic' oxy-1-ani1ide (d) 2.3-hydrox'ynaphthoic methyl-2'-anilide acid-2' -5'-dimeth-' acid-4'-chloro-1'- (e) 2.3-hydroxynaphthoicv acid-1'-naphthylamide.

There are obtained garnet dyeings which be come black when after-treated at theboil.

(7) By substituting for the 7.5 grams of 2.3-

hydroxynaphthoic acid anilide used in Example 5 the corresponding quantity of 2.3-hydroxynaphthoic acid-1'-methyl-2 ani1ide or 2.3-hydroxynaphthoic acid-1-methoxy 2-anilide, there are likewise obtained garnet dyeings which turn black when after-treated in a boiling bath in the manner disclosed in the foregoing examples.

Since an object of the present invention is to provide dyestuffs of good fastness properties, which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formula appearing in the appended claims contain. no substituents which are known to render organic compounds soluble inv water or alkalies' and which tend to depreciate the fastness of the dyestuffs to alkalies. Substituents of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

We claim: i

1. As new products the water-insoluble azodyestuffs of the following probable formula:

H oo.NH.R

wherein the R's represent residues of the benzene or naphthalene series, said products being dark powders and yielding, when produced on the fiber, black dyeings. 2. As new products the water-insoluble azodyestuffs of the following probable formula:

wherein the R's representresidues of the benzene or naphthalene series, said products being dark powders andyielding, when produced on the fiber, black dyeings. 1

3. As new products the water-insoluble azodyestuffs of thegfollowing probable formula:

wherein Rrepresents'a residue of the benzene series, said products being dark powders and yielding, when produced on the fiber, black dyeings. 1 i v 4..As anew product the water-insoluble azodyestuff of the following probable formula:

said product being a dark powderand yielding,

when produced on the fiber, a black dyeing.

10. Fiber dyed with a dyestufi as claimed in c1aim9.

ERWIN HOFFA. PAUL JGRG.

H CO.NH.R 100 V 

